Hafnium lanthanide oxynitride films

ABSTRACT

Electronic apparatus and methods of forming the electronic apparatus include a hafnium lanthanide oxynitride film on a substrate for use in a variety of electronic systems. The hafnium lanthanide oxynitride film may be structured as one or more monolayers. Metal electrodes may be disposed on a dielectric containing a hafnium lanthanide oxynitride film.

RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 11/515,143, filed 31 Aug. 2006 now U.S. Pat. No. 7,563,730, which isincorporated herein by reference in its entirety.

This application is related to the and commonly assigned applicationsU.S. application Ser. No. 10/229,903, now entitled “ATOMIC LAYERDEPOSITED HfSiON DIELECTRIC FILMS WHEREIN EACH PRECURSOR ISINDEPENDENTLY PULSED,” filed on 28 Aug. 2002, now U.S. Pat. No.7,199,023, U.S. application Ser. No. 11/216,474, entitled “LANTHANUMALUMINUM OXYNITRIDE DIELECTRIC FILMS,” filed on 31 Aug. 2005, U.S.application Ser. No. 11/355,490, entitled “CONDUCTIVE LAYERS FOR HAFNIUMSILICON OXYNITRIDE FILMS,” filed on 16 Feb. 2006, U.S. application Ser.No. 11/010,529, now entitled “LANTHANUM HAFNIUM OXIDE DIELECTRICS,”filed on 13 Dec. 2004, now U.S. Pat. No. 7,235,501, and U.S. applicationSer. No. 10/352,507, entitled “Atomic layer deposition of metaloxynitride layers as gate dielectrics and semiconductor devicestructures utilizing metal oxynitride layer,” filed on 27 Jan. 2003,which applications are incorporated herein by reference.

This application is also related to co-pending and commonly assignedU.S. application Ser. No. 11/514,655, now entitled “TANTALUM ALUMINUMOXYNITRIDE HIGH-K DIELECTRIC”, filed 31 Aug. 2006, U.S. application Ser.No. 11/514,533, entitled “SILICON LANTHANIDE OXYNITRIDE FILMS”, filed 31Aug. 2006, U.S. application Ser. No. 11/514,601, entitled “TANTALUMSILICON OXYNITRIDE HIGH-K DIELECTRICS AND METAL GATES”, filed 31 Aug.2006, U.S. application Ser. No. 11/514,545, entitled “TANTALUMLANTHANIDE OXYNITRIDE FILMS,” filed 31 Aug. 2006, now U.S. Pat. No.7,544,604, U.S. application Ser. No. 11/498,578, entitled “DEPOSITION OFZrAlON FILMS”, filed 3 Aug. 2006, U.S. application Ser. No. 11/515,114,now entitled “HAFNIUM TANTALUM OXYNITRIDE HIGH-K DIELECTRIC AND METALGATES”, filed 31 Aug. 2006, and U.S. application Ser. No. 11/514,558,now entitled “HAFNIUM ALUMINUM OXYNITRIDE HIGH-K DIELECTRIC AND METALGATES”, filed 31 Aug. 2006, which patent applications are incorporatedherein by reference.

TECHNICAL FIELD

This disclosure relates generally to semiconductor devices and devicefabrication.

BACKGROUND

The semiconductor device industry has a market driven need to reduce thesize of devices used in products such as processor chips, mobiletelephones, and memory devices such as dynamic random access memories(DRAMs). Currently, the semiconductor industry relies on the ability toreduce or scale the dimensions of its basic devices. This device scalingincludes scaling a dielectric layer in devices such as, for example,capacitors and silicon-based metal oxide semiconductor field effecttransistors (MOSFETs), which have primarily been fabricated usingsilicon dioxide. A thermally grown amorphous SiO₂ provides anelectrically and thermodynamically stable material, where the interfaceof the SiO₂ layer with underlying silicon provides a high qualityinterface as well as superior electrical isolation properties. However,increased scaling and other requirements in microelectronic devices havecreated the need to use other materials as dielectric regions in avariety of electronic structures.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts an embodiment of an atomic layer deposition system forprocessing a hafnium lanthanide oxynitride film.

FIG. 2A shows a flow diagram of features of an embodiment for forming ahafnium lanthanide oxynitride film using atomic layer deposition andnitridization.

FIG. 2B shows a flow diagram of features of an embodiment for forminghafnium lanthanide oxide using atomic layer deposition for nitridizationto a hafnium lanthanide oxynitride film.

FIG. 3 shows a flow diagram of features of an embodiment for forming ahafnium lanthanide oxynitride film using atomic layer deposition andoxidation.

FIG. 4 shows a flow diagram of features of an embodiment for forminghafnium lanthanide oxynitride film using atomic layer deposition andannealing.

FIGS. 5A-5E illustrate an embodiment of a process for forming a metalsubstituted electrode.

FIG. 6 illustrates a flow diagram of features of an embodiment of ametal substitution technique.

FIGS. 7A-7D illustrate an embodiment of a process for forming a selfaligned conductive layer.

FIG. 8 illustrates an embodiment of a method for forming a self alignedmetal gate on high-κ gate dielectrics containing a hafnium lanthanideoxynitride film.

FIG. 9 illustrates a wafer containing integrated circuits having ahafnium lanthanide oxynitride film.

FIG. 10 shows an embodiment of a transistor having a dielectric layerincluding a hafnium lanthanide oxynitride film.

FIG. 11 shows an embodiment of a floating gate transistor having adielectric layer including a hafnium lanthanide oxynitride film.

FIG. 12 shows an embodiment of a capacitor having a dielectric layerincluding a hafnium lanthanide oxynitride film.

FIG. 13 depicts an embodiment of a dielectric layer having multiplelayers including a hafnium lanthanide oxynitride layer.

FIG. 14 is a simplified diagram for an embodiment of a controllercoupled to an electronic device having a dielectric layer including ahafnium lanthanide oxynitride film.

FIG. 15 illustrates a diagram for an embodiment of an electronic systemincluding devices with a dielectric film including a hafnium lanthanideoxynitride film.

DETAILED DESCRIPTION

The following detailed description refers to the accompanying drawingsthat show, by way of illustration, various embodiments of the presentinvention. These embodiments are described in sufficient detail toenable those skilled in the art to practice these and other embodiments.Other embodiments may be utilized, and structural, logical, andelectrical changes may be made to these embodiments. The variousembodiments are not necessarily mutually exclusive, as some embodimentscan be combined with one or more other embodiments to form newembodiments. The following detailed description is, therefore, not to betaken in a limiting sense.

In the following description, the terms wafer and substrate may be usedinterchangeably to refer generally to any structure on which integratedcircuits are formed and also to such structures during various stages ofintegrated circuit fabrication. The term substrate is understood toinclude a semiconductor wafer. The term substrate is also used to referto semiconductor structures during processing and may include otherlayers that have been fabricated thereupon. Both wafer and substrateinclude doped and undoped semiconductors, epitaxial semiconductor layerssupported by a base semiconductor or insulator, as well as othersemiconductor structures well known to one skilled in the art. The termconductor is understood to generally include n-type and p-typesemiconductors and the term insulator or dielectric is defined toinclude any material that is less electrically conductive than thematerials referred to as conductors. The following detailed descriptionis, therefore, not to be taken in a limiting sense.

To scale a dielectric region to reduce feature sizes to provide highdensity electronic devices, the dielectric region should have a reducedequivalent oxide thickness (t_(eq)). The equivalent oxide thicknessquantifies the electrical properties, such as capacitance, of adielectric in terms of a representative physical thickness. t_(eq) isdefined as the thickness of a theoretical SiO₂ layer that would berequired to have the same capacitance density as a given dielectric,ignoring leakage current and reliability considerations.

A SiO₂ layer of thickness, t, deposited on a silicon surface will have at_(eq) larger than its thickness, t. This t_(eq) results from thecapacitance in the surface on which the SiO₂ is deposited due to theformation of a depletion/inversion region. This depletion/inversionregion can result in t_(eq) being from 3 to 6 Angstroms (Å) larger thanthe SiO₂ thickness, t. Thus, with the semiconductor industry driving tosomeday scale a gate dielectric equivalent oxide thickness to less than10 Å, the physical thickness requirement for a SiO₂ layer used for agate dielectric may need to be approximately 4 to 7 Å. Additionalrequirements on a SiO₂ layer would depend on the electrode used inconjunction with the SiO₂ dielectric. Using a conventional polysiliconelectrode may result in an additional increase in t_(eq) for the SiO₂layer. Thus, designs for future devices may be directed towards aphysical SiO₂ dielectric layer of about 5 Å or less. Such a smallthickness requirement for a SiO₂ oxide layer creates additionalproblems.

Silicon dioxide is used as a dielectric layer in devices, in part, dueto its electrical isolation properties in a SiO₂—Si based structure.This electrical isolation is due to the relatively large band gap ofSiO₂ (8.9 eV), making it a good insulator from electrical conduction.Significant reductions in its band gap may eliminate it as a materialfor a dielectric region in an electronic device. As the thickness of aSiO₂ layer decreases, the number of atomic layers or monolayers of thematerial decreases. At a certain thickness, the number of monolayerswill be sufficiently small that the SiO₂ layer will not have a completearrangement of atoms as in a larger or bulk layer. As a result ofincomplete formation relative to a bulk structure, a thin SiO₂ layer ofonly one or two monolayers may not form a full band gap. The lack of afull band gap in a SiO₂ dielectric may cause an effective short betweenan underlying electrode and an overlying electrode. This undesirableproperty sets a limit on the physical thickness to which a SiO₂ layercan be scaled. The minimum thickness due to this monolayer effect isthought to be about 7-8 Å. Therefore, for future devices to have at_(eq) less than about 10 Å, other dielectrics than SiO₂ need to beconsidered for use as a dielectric region in such future devices.

In many cases, for a typical dielectric layer, the capacitance isdetermined as one for a parallel plate capacitance: C=κε₀A/t, where κ isthe dielectric constant, ε₀ is the permittivity of free space, A is thearea of the capacitor, and t is the thickness of the dielectric. Thethickness, t, of a material is related to its t_(eq) for a givencapacitance, with SiO₂ having a dielectric constant κ_(ox)=3.9, ast=(κ/κ_(ox))t _(eq)=(κ/3.9)t _(eq).Thus, materials with a dielectric constant greater than that of SiO₂,3.9, will have a physical thickness that can be considerably larger thana desired t_(eq), while providing the desired equivalent oxidethickness. For example, an alternative dielectric material with adielectric constant of 10 could have a thickness of about 25.6 Å toprovide a t_(eq) of 10 Å, not including any depletion/inversion layereffects. Thus, a reduced equivalent oxide thickness for transistors canbe realized by using dielectric materials with higher dielectricconstants than SiO₂.

The thinner equivalent oxide thickness required for lower deviceoperating voltages and smaller device dimensions may be realized by asignificant number of materials, but additional fabricating requirementsmake determining a suitable replacement for SiO₂ difficult. The currentview for the microelectronics industry is still for silicon-baseddevices. This may require that the dielectric material employed be grownon a silicon substrate or a silicon layer, which places significantconstraints on the substitute dielectric material. During the formationof the dielectric on the silicon layer, there exists the possibilitythat a small layer of SiO₂ could be formed in addition to the desireddielectric. The result would effectively be a dielectric layerconsisting of two sublayers in parallel with each other and the siliconlayer on which the dielectric is formed. In such a case, the resultingcapacitance would be that of two dielectrics in series. As a result, thet_(eq) of the dielectric layer would be the sum of the SiO₂ thicknessand a multiplicative factor of the thickness, t, of the dielectric beingformed, written ast _(eq) =t _(SiO) ₂ +(κ_(ox)/κ)t.Thus, if a SiO₂ layer is formed in the process, the t_(eq) is againlimited by a SiO₂ layer. In the event that a barrier layer is formedbetween the silicon layer and the desired dielectric in which thebarrier layer prevents the formation of a SiO₂ layer, the t_(eq) wouldbe limited by the layer with the lowest dielectric constant. However,whether a single dielectric layer with a high dielectric constant or abarrier layer with a higher dielectric constant than SiO₂ is employed,the layer interfacing with the silicon layer should provide a highquality interface.

Using SiO₂ as a dielectric layer in a device has allowed the formationof a SiO₂ layer that results in an amorphous dielectric. Having anamorphous structure for a dielectric provides for reducing problems ofleakage current associated with grain boundaries in polycrystallinedielectrics that provide high leakage paths. Additionally, grain sizeand orientation changes throughout a polycrystalline dielectric cancause variations in the film's dielectric constant, along withuniformity and surface topography problems. Materials having a highdielectric constant relative to SiO₂ may also have a crystalline form,at least in a bulk configuration. The best candidates for replacing SiO₂as a dielectric in a device are those that can be fabricated as a thinlayer with an amorphous form and that have high dielectric constants.

Capacitor applications have used high-κ dielectric materials, which areinsulating materials having a dielectric constant greater than silicondioxide. Such high-κ dielectric materials include silicon oxynitride(SiON, κ˜6), alumina (Al₂O₃, κ˜9), and oxide/nitride composites(SiO₂/Si₃N₄, κ˜6). Other possible candidates include metal oxides(κ˜8-80), nitrides (κ˜7-30), oxynitrides (κ˜6-25), silicates (κ˜6-20),carbides (κ˜6-15), and complex titanates (κ˜>100). Factors for selectingappropriate materials include physical, chemical and thermal stabilityas well as etch-ability and stoichiometric reproducibility. In fieldeffect transistor (FET) applications, there are other factors toconsider while addressing device scalability. The selected dielectricshould provide stable amorphous and adherent films in the thicknessrange of 1 nm to 100 nm at temperatures ranging from room temperature to1000° C. A relatively defect-free composition that is uniform andreproducible with a fixed charge density and trap density of less than10¹¹ cm⁻² in films of such composition is a factor. A factor includesdielectric materials that provide a stable non-reactive interface with asilicon substrate such that the interface has an interface state densitymuch less than 10¹¹ cm⁻². Such interface state densities may occur whensilicon bonds at the interface are saturated with high strength covalentbonds with molecular elements of the dielectric material. Another factordeals with current transport through the dielectric that should becontrolled by tunneling, which is independent of temperature, ratherthan by trap-assisted thermally dependent transport. The conductivity ofthe dielectric should be equal to or lower than SiO₂ films when voltageis stressed to a field strength of 5×10⁶ V/cm. To address the currenttransport, a dielectric material having a bandgap greater than 5 eV andhaving an electron and hole barrier height greater than 2 eV at asilicon interface may be considered. An additional factor to consider isusing dielectric materials with a destructive breakdown strength greaterthan 6×10⁶ V/cm. Other factors for selecting a dielectric material foruse in a variety of electronic devices, such as for the dielectric inFETs, relates to processing characteristics. Such processingcharacteristics include compatibility with gate material, selectiveetch-ability, chemical inertness to contaminants, dopant and postprocessing environments (temperature, pressure, ambients), and intrinsicproperties associated with annealing of defects/damages caused bypost-processing such as ion-implantation, plasma-radiation, andgate/back-end processing.

In various embodiments, mixed metal oxynitrides (with silicon includedas a metal) are constructed as dielectric films in a variety ofelectronic devices and systems. Most oxynitrides are thermally stableand can integrate into semiconductor device processing. With nitrogenconcentration in an oxynitride film at 30% or higher, such oxynitridesare chemically inert. With processing conditions controlled to provideappropriately low partial pressures of hydrogen and ON ions, oxynitridefilms with a wide range of nitrogen to oxygen ratio can be depositedover a silicon substrate with low fixed charge and interface statesdensity. On the other hand, charge trapping and transportcharacteristics are dependent on relative ratio of nitrogen to oxygencontent in the constructed film. Films with nitrogen concentration twicethat of oxygen (for example, approximately 40 atomic per cent nitrogen,approximately 20 atomic per cent oxygen, and approximately 40 atomic percent metal or silicon) have a lower bandgap, higher trap density, andtransport characteristics dominated by Frenkel-Poole conduction. Suchmaterials may not be well suited for gate dielectric applications.However, such films exhibit higher κ values. With increasing oxygenconcentration in oxynitride films, the bandgap is raised, currentleakage is reduced, and the low frequency κ value is also somewhatreduced. In addition with increasing oxygen concentration, the trapdensity is reduced, the trap energy depth is increased, and the carriertransport ceases to be trap-assisted, exhibits tunneling conduction, andhas a weak temperature dependence, if any. In various embodiments, adielectric layer includes an oxynitride film having approximately 30atomic % oxygen and approximately 30-35 atomic % nitrogen. With highenough nitrogen content, oxygen-vacancy induced defects in films isnegligible when compared with metal oxides.

Silicon oxynitride (SiON) has been used as a gate dielectric and gateinsulator for a non-volatile FET device. Silicon oxynitride at acomposition range of Si₂ON₂ exhibits a dielectric constant of 6.5 and abandgap of approximately 6.5 eV compared to a stoichiometric nitride ofκ=7.5 and a bandgap of 5.1 eV. Aluminum oxynitride (AlON) is expected tohave a bandgap greater than 5 eV with a κ value similar to SiON.Compared to SiON, metal oxynitrides such as ZrON, HfON, LaON, and TaONand other single metal oxynitrides are expected to have a lower bandgap.

In various embodiments, bimetal (or metal/silicon) oxynitrides based onSi, Al, Hf, La, and Ta are used as dielectric films in a variety ofelectronic devices and systems. These bimetal oxynitrides may provide abandgap range from 5 eV to greater than 7 eV. Estimates for bandgapsinclude a bandgap of Si—Al—ON of greater than 7 eV, a bandgap ofSi—Hf—ON of about 6.9 eV, a bandgap of Al—Hf—ON of about 6.8 eV, abandgap of Si—Ta—ON of about 6 eV, a bandgap of Al—Ta—ON of about 6 eV.Bimetal oxynitrides Hf—Ta—ON, Hf—La—ON, Al—La—ON, Ta—La—ON, and Si—La—ONare estimated to exhibit significantly lower bandgaps. The κ value forSi—Al—ON is estimated at approximately 7 to 8, while the κ values forthe other oxynitrides of this group are estimated to be in the rangefrom about 15 to 25.

In an embodiment, a film of hafnium lanthanide oxynitride may be used asa dielectric layer for application in a variety of electronic devices,replacing the use of silicon oxide to provide a higher dielectricconstant. The hafnium lanthanide oxynitride film may be formed as ahafnium lanthanum oxynitride film. In other embodiments, one of morelanthanides may be used to form a hafnium lanthanide oxynitride film.The lanthanide, represented by the expression Ln, may include one ormore elements from the lanthanide group consisting of lanthanum (La),cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm),samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium(Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), andlutetium (Lu). In various embodiments, a dielectric layer may beconstructed containing hafnium lanthanide oxynitride formed using atomiclayer deposition with a metal electrode formed in contact with thedielectric layer. The metal electrode may be formed by atomic layerdeposition. The metal electrode may be formed by substituting a desiredmetal material for a previously disposed substitutable material. Themetal electrode may be formed as a self aligned metal electrode on andcontacting the dielectric layer. The metal electrode may be formed onthe dielectric layer using a previously disposed sacrificial carbonlayer on the dielectric layer and sacrificial carbon sidewall spacersadjacent to the sacrificial carbon layer.

The term hafnium lanthanide oxynitride is used herein with respect to acomposition that essentially consists of hafnium, lanthanide, oxygen,and nitrogen in a form that may be stoichiometric, non-stoichiometric,or a combination of stoichiometric and non-stoichiometric. In anembodiment, the lanthanide may be lanthanum. Alternatively, thelanthanide may be one or more elements from the lanthanide group ofelements. A hafnium lanthanide oxynitride film may also be referred toas a hafnium lanthanide oxygen nitrogen film. Other nomenclature for acomposition that essentially consists of hafnium, lanthanide, oxygen,and nitrogen may be known to those skilled in the art. In an embodiment,hafnium lanthanide oxynitride may be formed substantially as astoichiometric hafnium lanthanide oxynitride film. In an embodiment,hafnium lanthanide oxynitride may be formed substantially as anon-stoichiometric hafnium lanthanide oxynitride film. In an embodiment,hafnium lanthanide oxynitride may be formed substantially as acombination film of non-stoichiometric hafnium lanthanide oxynitride andstoichiometric hafnium lanthanide oxynitride. Herein, a hafniumlanthanide oxynitride composition may be expressed as HfLnON,HfLnON_(x), Hf_(x)Ln_(y)O_(z)N_(r), or other equivalent form. Herein, ahafnium lanthanum oxynitride composition may be expressed as HfLaON,HfLaON_(r), Hf_(x)La_(y)O_(z)N_(r), or other equivalent form. Theexpression HfLnON or its equivalent forms may be used to include HfLnONin a form that is stoichiometric, non-stoichiometric, or a combinationof stoichiometric and non-stoichiometric hafnium lanthanide oxynitride.The expressions LnO, LnO_(z), or its equivalent forms may be used toinclude lanthanide oxide in a form that is stoichiometric,non-stoichiometric, or a combination of stoichiometric andnon-stoichiometric. With respect to forms that are stoichiometric,non-stoichiometric, or a combination of stoichiometric andnon-stoichiometric, expressions such as LnN, LaO, LaN, HfON, LnON, LaON,LaO_(z), LaN_(r), HfO_(t), HfN_(s), HfON_(r), LnON_(r), LaON_(r) etc.may be used in a similar manner as LnO_(z). In various embodiments, ahafnium lanthanide oxynitride film may be doped with elements orcompounds other than hafnium, lanthanide, oxygen, and nitrogen.

In an embodiment, a hafnium lanthanide oxynitride dielectric film may beformed using atomic layer deposition (ALD). Forming such structuresusing atomic layer deposition may allow control of transitions betweenmaterial layers. As a result of such control, atomic layer depositedhafnium lanthanide oxynitride dielectric films can have an engineeredtransition with a surface on which it is formed.

ALD, also known as atomic layer epitaxy (ALE), is a modification ofchemical vapor deposition (CVD) and is also called “alternativelypulsed-CVD.” In ALD, gaseous precursors are introduced one at a time tothe substrate surface mounted within a reaction chamber (or reactor).This introduction of the gaseous precursors takes the form of pulses ofeach gaseous precursor. In a pulse of a precursor gas, the precursor gasis made to flow into a specific area or region for a short period oftime. Between the pulses, the reaction chamber may be purged with a gas,where the purging gas may be an inert gas. Between the pulses, thereaction chamber may be evacuated. Between the pulses, the reactionchamber may be purged with a gas and evacuated.

In a chemisorption-saturated ALD (CS-ALD) process, during the firstpulsing phase, reaction with the substrate occurs with the precursorsaturatively chemisorbed at the substrate surface. Subsequent pulsingwith a purging gas removes precursor excess from the reaction chamber.

The second pulsing phase introduces another precursor on the substratewhere the growth reaction of the desired film takes place. Subsequent tothe film growth reaction, reaction byproducts and precursor excess arepurged from the reaction chamber. With favorable precursor chemistrywhere the precursors absorb and react with each other aggressively onthe substrate, one ALD cycle can be performed in less than one second inproperly designed flow type reaction chambers. Typically, precursorpulse times range from about 0.5 sec to about 2 to 3 seconds. Pulsetimes for purging gases may be significantly longer, for example, pulsetimes of about 5 to about 30 seconds.

In ALD, the saturation of all the reaction and purging phases makes thegrowth self-limiting. This self-limiting growth results in large areauniformity and conformality, which has important applications for suchcases as planar substrates, deep trenches, and in the processing ofporous silicon and high surface area silica and alumina powders. Atomiclayer deposition provides control of film thickness in a straightforwardmanner by controlling the number of growth cycles.

The precursors used in an ALD process may be gaseous, liquid or solid.However, liquid or solid precursors should be volatile. The vaporpressure should be high enough for effective mass transportation. Also,solid and some liquid precursors may need to be heated inside the atomiclayer deposition system and introduced through heated tubes to thesubstrates. The necessary vapor pressure should be reached at atemperature below the substrate temperature to avoid the condensation ofthe precursors on the substrate. Due to the self-limiting growthmechanisms of ALD, relatively low vapor pressure solid precursors can beused, though evaporation rates may vary somewhat during the processbecause of changes in their surface area.

There are several other characteristics for precursors used in ALD. Theprecursors should be thermally stable at the substrate temperature,because their decomposition may destroy the surface control of the ALDmethod that relies on the reaction of the precursor at the substratesurface. A slight decomposition, if slow compared to the ALD growth, maybe tolerated.

The precursors should chemisorb on or react with the surface, though theinteraction between the precursor and the surface as well as themechanism for the adsorption is different for different precursors. Themolecules at the substrate surface should react aggressively with thesecond precursor to form the desired solid film. Additionally,precursors should not react with the film to cause etching, andprecursors should not dissolve in the film. Using highly reactiveprecursors in ALD contrasts with the selection of precursors forconventional CVD.

The by-products in the reaction should be gaseous in order to allowtheir easy removal from the reaction chamber. Further, the by-productsshould not react or adsorb on the surface.

In a reaction sequence ALD (RS-ALD) process, the self-limiting processsequence involves sequential surface chemical reactions. RS-ALD relieson chemistry between a reactive surface and a reactive molecularprecursor. In an RS-ALD process, molecular precursors are pulsed intothe ALD reaction chamber separately. A metal precursor reaction at thesubstrate may be followed by an inert gas pulse to remove excessprecursor and by-products from the reaction chamber prior to pulsing thenext precursor of the fabrication sequence.

By RS-ALD, films can be layered in equal metered sequences that may allbe identical in chemical kinetics, deposition per cycle, composition,and thickness. RS-ALD sequences generally deposit less than a full layerper cycle. Typically, a deposition or growth rate of about 0.25 to about2.00 Å per RS-ALD cycle may be realized.

Processing by RS-ALD provides continuity at an interface avoiding poorlydefined nucleating regions that are typical for chemical vapordeposition (<20 Å) and physical vapor deposition (<50 Å), conformalityover a variety of substrate topologies due to its layer-by-layerdeposition technique, use of low temperature and mildly oxidizingprocesses, lack of dependence on the reaction chamber, growth thicknessdependent solely on the number of cycles performed, and ability toengineer multilayer laminate films with a resolution of one to twomonolayers. RS-ALD processes allow for deposition control on the orderof monolayers and the ability to deposit monolayers of amorphous films.

Herein, a sequence refers to the ALD material formation based on an ALDreaction of a precursor with its reactant precursor. For example,forming hafnium nitride from a HfCl₄ precursor and NH₃, as its reactantprecursor, includes a hafnium/nitrogen sequence. In various ALDprocesses that form a nitride or a composition that contains nitrogen, areactant precursor that contains nitrogen is used to supply nitrogen.Herein, a precursor that contains nitrogen and that supplies nitrogen tobe incorporated in the ALD composition formed, which may be used in anALD process with precursors supplying the other elements in the ALDcomposition, is referred to as a nitrogen reactant precursor. In theabove example, NH₃ is a nitrogen reactant precursor. Similarly, an ALDsequence for a metal oxide may be referenced with respect to the metaland oxygen. For example, an ALD sequence for hafnium oxide may also bereferred to as a hafnium/oxygen sequence. In various ALD processes thatform an oxide or a composition that contains oxygen, a reactantprecursor that contains oxygen is used to supply the oxygen. Herein, aprecursor that contains oxygen and that supplies oxygen to beincorporated in the ALD composition formed, which may be used in an ALDprocess with precursors supplying the other elements in the ALDcomposition, is referred to as an oxygen reactant precursor. With an ALDprocess using HfCl₄ and water vapor to form hafnium oxide, water vaporis an oxygen reactant precursor. An ALD cycle may include pulsing aprecursor, pulsing a purging gas for the precursor, pulsing a reactantprecursor, and pulsing the reactant precursor's purging gas. An ALDcycle may include pulsing a precursor, evacuating the reactant chamber,pulsing a reactant precursor, and evacuating the reactant chamber. AnALD cycle may include pulsing a precursor, pulsing a purging gas for theprecursor and evacuating the reactant chamber, pulsing a reactantprecursor, and pulsing the reactant precursor's purging gas andevacuating the reactant chamber.

In forming a layer of a metal species, an ALD sequence may deal withpulsing a reactant precursor to the substrate surface on which ametal-containing species has been absorbed such that the reactantprecursor reacts with the metal-containing species resulting in thedeposited metal and a gaseous by-product that can be removed during thesubsequent purging/evacuating process. Alternatively, in forming a layerof a metal species, an ALD sequence may deal with reacting a precursorcontaining the metal species with a substrate surface. A cycle for sucha metal forming sequence may include pulsing a purging gas after pulsingthe precursor containing the metal species to deposit the metal.Additionally, deposition of a semiconductor material may be realized ina manner similar to forming a layer of a metal, given the appropriateprecursors for the semiconductor material.

In an ALD formation of a composition having more than two elements, acycle may include a number of sequences to provide the elements of thecomposition. For example, a cycle for an ALD formation of an ABO_(x)composition may include sequentially pulsing a first precursor/a purginggas for the first precursor/a first reactant precursor/the firstreactant precursor's purging gas/a second precursor/a purging gas forthe second precursor/a second reactant precursor/the second reactantprecursor's purging gas, which may be viewed as a cycle having twosequences. In an embodiment, a cycle may include a number of sequencesfor element A and a different number of sequences for element B. Theremay be cases in which ALD formation of an ABO_(x) composition uses oneprecursor that contains the elements A and B, such that pulsing the ABcontaining precursor followed by its reactant precursor onto a substratemay include a reaction that forms ABO_(x) on the substrate to provide anAB/oxygen sequence. A cycle of an AB/oxygen sequence may include pulsinga precursor containing A and B, pulsing a purging gas for the precursor,pulsing an oxygen reactant precursor to the A/B precursor, and pulsing apurging gas for the reactant precursor. A cycle may be repeated a numberof times to provide a desired thickness of the composition. In anembodiment, a cycle for an ALD formation of the quaternary composition,hafnium lanthanide oxygen nitrogen, may include sequentially pulsing afirst precursor/a purging gas for the first precursor/a first reactantprecursor/the first reactant precursor's purging gas/a secondprecursor/a purging gas for the second precursor/a second reactantprecursor/the second reactant precursor's purging gas/a thirdprecursor/a purging gas for the third precursor/a third reactantprecursor/the third reactant precursor's purging gas, which may beviewed as a cycle having three sequences. In an embodiment, a layersubstantially of a hafnium lanthanide oxynitride composition is formedon a substrate mounted in a reaction chamber using ALD in repetitivelanthanide/oxygen and hafnium/nitrogen sequences using precursor gasesindividually pulsed into the reaction chamber. In an embodiment, a layersubstantially of a hafnium lanthanide oxynitride composition is formedon a substrate mounted in a reaction chamber using ALD in repetitivelanthanide/nitrogen and hafnium/oxygen sequences using precursor gasesindividually pulsed into the reaction chamber. In an embodiment, asubstantially hafnium lanthanide oxynitride composition is formed by ALDhaving approximately 30% nitrogen and 30% oxygen concentrations in theresultant HfLnON dielectric film.

FIG. 1 shows an embodiment of an atomic layer deposition system 100 forprocessing a dielectric film containing a Hf_(x)Ln_(y)O_(z)N_(r) layer.The elements depicted are those elements necessary for discussion ofvarious embodiments for forming HfLnON such that those skilled in theart may practice embodiments of the present invention without undueexperimentation. A substrate 110 is located inside a reaction chamber120 of ALD system 100. Also located within reaction chamber 120 is aheating element 130, which is thermally coupled to substrate 110 tocontrol the substrate temperature. A gas-distribution fixture 140introduces precursor gases to the substrate 110. Each precursor gasoriginates from individual gas sources 150-155 whose flow is controlledby mass-flow controllers 156-161, respectively. Gas sources 150-155provide a precursor gas either by storing the precursor as a gas or byproviding a location and apparatus for evaporating a solid or liquidmaterial to form the selected precursor gas. Furthermore, additional gassources may be included, one for each metal precursor employed and onefor each reactant precursor associated with each metal precursor.

Also included in the ALD system are purging gas sources 163, 164, eachof which is coupled to mass-flow controllers 166, 167, respectively.Furthermore, additional purging gas sources may be constructed in ALDsystem 100, one purging gas source for each precursor gas. For a processthat uses the same purging gas for multiple precursor gases, lesspurging gas sources are required for ALD system 100. Gas sources 150-155and purging gas sources 163-164 are coupled by their associatedmass-flow controllers to a common gas line or conduit 170, which iscoupled to the gas-distribution fixture 140 inside reaction chamber 120.Gas conduit 170 is also coupled to vacuum pump, or exhaust pump, 181 bymass-flow controller 186 to remove excess precursor gases, purginggases, and by-product gases at the end of a purging sequence from gasconduit 170.

Vacuum pump, or exhaust pump, 182 is coupled by mass-flow controller 187to remove excess precursor gases, purging gases, and by-product gases atthe end of a purging sequence from reaction chamber 120. Forconvenience, control displays, mounting apparatus, temperature sensingdevices, substrate maneuvering apparatus, and necessary electricalconnections as are known to those skilled in the art are not shown inFIG. 1. The use, construction and fundamental operation of reactionchambers for deposition of films are understood by those of ordinaryskill in the art of semiconductor fabrication. Embodiments of thepresent invention may be practiced on a variety of such reactionchambers without undue experimentation. Furthermore, one of ordinaryskill in the art will comprehend the necessary detection, measurement,and control techniques in the art of semiconductor fabrication uponreading the disclosure.

In an embodiment, a hafnium lanthanide oxynitride layer may bestructured as one or more monolayers. A film of hafnium lanthanideoxynitride, structured as one or more monolayers, may have a thicknessthat ranges from a monolayer to thousands of angstroms or more. The filmmay be processed using atomic layer deposition. Embodiments of an atomiclayer deposited hafnium lanthanide oxynitride layer have a largerdielectric constant than silicon dioxide. Such dielectric layers providea significantly thinner equivalent oxide thickness compared with asilicon oxide layer having the same physical thickness. Alternatively,such dielectric layers provide a significantly thicker physicalthickness than a silicon oxide layer having the same equivalent oxidethickness. This increased physical thickness aids in reducing leakagecurrent.

Prior to forming the hafnium lanthanide oxynitride film using ALD, thesurface on which the hafnium lanthanide oxynitride film is to bedeposited may undergo a preparation stage. The surface may be thesurface of a substrate for an integrated circuit. In an embodiment, thesubstrate used for forming a transistor may include a silicon or siliconcontaining material. In other embodiments, silicon germanium, germanium,gallium arsenide, silicon-on-sapphire substrates, or other suitablesubstrates may be used. A preparation process may include cleaning thesubstrate and forming layers and regions of the substrate, such asdrains and sources, prior to forming a gate dielectric in the formationof a metal insulator semiconductor (MIS) transistor. Alternatively,active regions may be formed after forming the dielectric layer,depending on the over-all fabrication process implemented. In anembodiment, the substrate is cleaned to provide an initial substratedepleted of its native oxide. In an embodiment, the initial substrate iscleaned also to provide a hydrogen-terminated surface. In an embodiment,a silicon substrate undergoes a final hydrofluoric (HF) rinse prior toALD processing to provide the silicon substrate with ahydrogen-terminated surface without a native silicon oxide layer.

Cleaning immediately preceding atomic layer deposition aids in reducingan occurrence of silicon oxide as an interface between a silicon-basedsubstrate and a hafnium lanthanide oxynitride dielectric formed usingthe atomic layer deposition process. The material composition of aninterface layer and its properties are typically dependent on processconditions and the condition of the substrate before forming thedielectric layer. Though the existence of an interface layer mayeffectively reduce the dielectric constant associated with thedielectric layer and its substrate interface layer, a SiO₂ interfacelayer or other composition interface layer may improve the interfacedensity, fixed charge density, and channel mobility of a device havingthis interface layer.

The sequencing of the formation of the regions of an electronic device,such as a transistor, being processed may follow typical sequencing thatis generally performed in the fabrication of such devices as is wellknown to those skilled in the art. Included in the processing prior toforming a dielectric may be the masking of substrate regions to beprotected during the dielectric formation, as is typically performed insemiconductor fabrication. In an embodiment, an unmasked region includesa body region of a transistor; however, one skilled in the art willrecognize that other semiconductor device structures may utilize thisprocess.

In various embodiments, between each pulsing of a precursor used in anatomic layer deposition process, a purging gas may be pulsed into theALD reaction chamber. Between each pulsing of a precursor, the ALDreactor chamber may be evacuated using vacuum techniques as is known bythose skilled in the art. Between each pulsing of a precursor, a purginggas may be pulsed into the ALD reaction chamber and the ALD reactorchamber may be evacuated.

In an embodiment, an ALD cycle for forming HfLnON includes sequencingcomponent-containing precursors in the order of lanthanide, oxygen,hafnium, and nitrogen with appropriate purging between the differentcomponent-containing precursors. Full coverage or partial coverage of amonolayer on a substrate surface may be attained for pulsing of ametal-containing precursor. In an embodiment, an ALD cycle for formingHflnON includes sequencing the component-containing precursors invarious permutations. In an embodiment, an ALD cycle to form hafniumlanthanide oxynitride includes a number, x, of lanthanide/oxygensequences and a number, y, of hafnium/nitrogen sequences. In anembodiment, an ALD cycle to form hafnium lanthanide oxynitride includesa number, x, of lanthanide/nitrogen sequences and a number, y, ofhafnium/oxygen sequences. In an embodiment, the number of sequences xand y is selected to engineer the relative amounts of hafnium,lanthanide, oxygen, and nitrogen. In an embodiment, the number ofsequences x and y is selected to form a nitrogen-rich hafnium lanthanideoxynitride. In an embodiment, the number of sequences x and y areselected to form an oxygen-rich hafnium lanthanide oxynitride. Thehafnium lanthanide oxynitride may be engineered as a lanthanide-richdielectric relative to the amount of hafnium in the dielectric. Thehafnium lanthanide oxynitride may be engineered as a hafnium-richdielectric relative to the amount of lanthanide in the dielectric. Thepulsing of the individual component-containing precursors may beperformed independently in a non-overlapping manner using the individualgas sources 150-155 and flow controllers 156-161 of ALD system 100 ofFIG. 1.

Each precursor may be pulsed into the reaction chamber for apredetermined period, where the predetermined period can be setseparately for each precursor. Additionally, for various ALD formations,each precursor may be pulsed into the reaction chamber under separateenvironmental conditions. The substrate may be maintained at a selectedtemperature and the reaction chamber maintained at a selected pressureindependently for pulsing each precursor. Appropriate temperatures andpressures may be maintained, whether the precursor is a single precursoror a mixture of precursors.

A number of precursors containing a lanthanide may be used to providethe lanthanide to a substrate for an integrated circuit. In anembodiment, a precursor containing a lanthanide may include Ln(thd)₃(thd=2,2,6,6-tetramethyl-3,5-heptanedione)=Ln(C₁₁H₁₉O₂)₃. In anembodiment, a lanthanum-containing precursor is pulsed onto a substratein an ALD reaction chamber. A number of precursors containing lanthanumthat may be used includes, but is not limited to, La(thd)₃,La(N(SiMe₃)₂)₃=C₁₈H₅₄N₃LaSi₆, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)lanthanum (III) tetraglymeadduct=La(C₁₁H₁₉O₂)₃CH₃(OCH₂CH₂)₄OCH₃,trisethylcyclopentadionatolanthanum (La(EtCp)₃), andtrisdipyvaloylmethanatolanthanum (La(DPM)₃). Me is an abbreviation forCH₃, Et is an abbreviation for ethyl (CH₂CH₃), and Cp is an abbreviationfor a cyclopentadienyl ligand having the formula C₅H₅. In an embodiment,H₂ may be pulsed along with a La(EtCp)₃ precursor or a La(DPM)₃precursor to reduce carbon contamination in the fabricated film. Otherprecursors may be used in embodiments in which the lanthanide is otherthan lanthanum.

In various embodiments, after pulsing the lanthanide-containingprecursor and purging the reaction chamber of excess precursor andby-products from pulsing the precursor, a reactant precursor may bepulsed into the reaction chamber. The reactant precursor may be anoxygen reactant precursor that may include, but is not limited to, oneor more of water, atomic oxygen, molecular oxygen, ozone, hydrogenperoxide, a water—hydrogen peroxide mixture, alcohol, or nitrous oxide.In addition, the pulsing of the lanthanide precursor may use a pulsingperiod that provides uniform coverage of a monolayer on the surface ormay use a pulsing period that provides partial coverage of a monolayeron the surface during a lanthanide sequence.

A number of precursors containing hafnium may be used to provide thehafnium to a substrate for an integrated circuit. In an embodiment, aprecursor containing hafnium may include anhydrous hafnium nitride,Hf(NO₃)₄. In an embodiment using a Hf(NO₃)₄ precursor on ahydrogen-terminated silicon, the substrate temperature may be maintainedat a temperature ranging from about 160° C. to about 180° C. In anembodiment, a hafnium precursor may include HfCl₄. In an embodimentusing a HfCl₄ precursor, the substrate temperature may be maintained ata temperature ranging from about 180° C. to about 600° C. In anembodiment using a HfCl₄ precursor, the substrate temperature may bemaintained at a temperature ranging from about 300° C. to about 940° C.In an embodiment, a hafnium precursor may be HfI₄. In an embodimentusing a HfI₄ precursor, the substrate temperature may be maintained at atemperature of about 300° C. Hafnium oxide may be grown by ALD using aHf[N(CH₃)(C₂H₅)]₄, which may be known as a homoleptictetrakis(dialkylamino) hafnium(IV) compound, and water as an oxygenreactant. Other types of tetrakis(dialkylamino) hafnium compounds mayalso be used, such as hafnium tetrakis dimethylamine, Hf[N(CH₃)₂]₄, orhafnium tetrakis diethylamine, Hf[N(C₂H₅)₂]₄, as a hafnium-containingprecursor. In various embodiments, use of the individualhafnium-containing precursors is not limited to the temperature rangesof the above example embodiments. In addition, the pulsing of thehafnium precursor may use a pulsing period that provides uniformcoverage of a monolayer on the surface or may use a pulsing period thatprovides partial coverage of a monolayer on the surface during a hafniumsequence.

In various embodiments, nitrogen may be used as a purging gas and acarrier gas for one or more of the sequences used in the ALD formationof hafnium lanthanide oxynitride. Alternatively, hydrogen, argon gas, orother inert gases may be used as the purging gas. Excess precursor gasand reaction by-products may be removed by the purge gas. Excessprecursor gas and reaction by-products may be removed by evacuation ofthe reaction chamber using various vacuum techniques. Excess precursorgas and reaction by-products may be removed by the purge gas and byevacuation of the reaction chamber.

In an embodiment, after repeating a selected number of ALD cycles, adetermination is made as to whether the number of cycles equals apredetermined number to form the desired hafnium lanthanide oxynitridelayer. If the total number of cycles to form the desired thickness hasnot been completed, a number of cycles is repeated. In an embodiment,the thickness of a hafnium lanthanide oxynitride layer formed by atomiclayer deposition is determined by a fixed growth rate for the pulsingperiods and precursors used, set at a value such as N nm/cycle, and thenumber of cycles conducted. In an embodiment, depending on theprecursors used for ALD formation of a HfLnON film, the process isconducted in an ALD window, which is a range of temperatures in whichthe growth rate is substantially constant. In an embodiment, if such anALD window is not available, the ALD process is conducted at the sameset of temperatures for each ALD sequence in the process. For a desiredhafnium lanthanide oxynitride layer thickness, t, in an application, theALD process is repeated for t/N total cycles. Once the t/N cycles havecompleted, no further ALD processing for the hafnium lanthanideoxynitride layer is required. In an embodiment, a hafnium lanthanideoxynitride layer processed at relatively low temperatures associatedwith atomic layer deposition provides an amorphous layer.

In an embodiment, a HfLnON film may be grown to a desired thickness byrepetition of a process including atomic layer deposition of layers ofLnO and HfN and/or layers of HfO and LnN followed by annealing. In anembodiment, a base thickness may be formed according to variousembodiments such that forming a predetermined thickness of a HfLnON filmmay be conducted by forming a number of layers having the basethickness. As can be understood by one skilled in the art, determiningthe base thickness depends on the application and can be determinedduring initial processing without undue experimentation. Relativeamounts of hafnium, lanthanide, oxygen, and nitrogen in a HfLnON filmmay be controlled by regulating the relative thicknesses of theindividual layers of oxides and nitrides formed. In addition, relativeamounts of hafnium, lanthanide, oxygen, and nitrogen in a HfLnON filmmay be controlled by forming a layer of HfLnON as multiple layers ofdifferent base thickness and by regulating the relative thicknesses ofthe individual layers of oxides and nitrides formed in each base layerprior to annealing. As can be understood by those skilled in the art,particular effective growth rates for the engineered hafnium lanthanideoxynitride film can be determined during normal initial testing of theALD system used in processing a hafnium lanthanide oxynitride dielectricfor a given application without undue experimentation.

FIG. 2A shows a flow diagram of features of an embodiment for formingHfLnON using atomic layer deposition and nitridization. At 210, a layerof HfLnO is formed using atomic layer deposition. At 220, the layer ofHfLnO is subjected to a nitridization to form a HfLnON film. Thenitridization may be a high temperature nitridization. In thenitridization process, active nitrogen may be introduced by microwaveplasma. In the nitridization process, active nitrogen may be introducedby a NH₃ anneal. A high temperature nitridization is a nitridizingprocess that is performed at temperatures equal to or above 500° C. Invarious embodiments, HfLnO may be formed by atomic layer depositionusing ALD cycles of lanthanide/oxygen sequences and hafnium/oxygensequences. Depending on the amounts of lanthanide, hafnium, and oxygento be provided in the HfLaO film, the ALD cycle can be selected from anumber of different permutations of lanthanide/oxygen sequences andhafnium/oxygen sequences.

FIG. 2B shows a flow diagram of features of an embodiment for formingHfLnO using atomic layer deposition for nitridization to a HfLnON film.At 230, a layer of lanthanide oxide is formed on a substrate by atomiclayer deposition. At 240, a layer of hafnium oxide is formed by atomiclayer deposition on the layer of lanthanide oxide. At 250, the layers oflanthanide oxide and hafnium oxide are annealed to form a layer ofHfLnO. The order of forming LnO and HfO may be interchanged. The layerof HfLnO may be nitridized to form HfLnON. Alternatively, the layers oflanthanide oxide and hafnium oxide may be nitridized during theannealing process. In an embodiment, alternating layers of ALDlanthanide oxide and ALD hafnium oxide may be formed to a desiredthickness prior to nitridization. In an embodiment, a layer of ALDlanthanide oxide and a layer of ALD hafnium oxide may be formed, each toa desired thickness, the layers of ALD lanthanide oxide and ALD hafniumoxide nitridized to form a HfLnON layer. Then, a layer of ALD lanthanideoxide and a layer of ALD hafnium oxide may be formed on the HfLnONlayer, the layers of ALD lanthanide oxide and ALD hafnium oxidenitridized to form a HfLnON layer on and contiguous with the previouslyformed HfLnON layer. This process may be continued until the desiredthickness of HfLnON is formed.

In an embodiment, ALD LaO may be formed using a number of precursorscontaining lanthanum to provide the lanthanum to a substrate for anintegrated circuit. Such lanthanum-containing precursors include, butare not limited to, La(thd)₃, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)lanthanum (III) tetraglymeadduct, La(EtCp)₃, and La(DPM)₃. After pulsing the lanthanum-containingprecursor and purging the reaction chamber of excess precursor andby-products from pulsing the precursor, an oxygen reactant precursor maybe pulsed into the reaction chamber. The oxygen reactant precursor mayinclude, but is not limited to, one or more of water, atomic oxygen,molecular oxygen, ozone, hydrogen peroxide, a water—hydrogen peroxidemixture, alcohol, or nitrous oxide. After pulsing the oxygen-containingprecursor, the reaction chamber may be purged of excess precursor andby-products. In addition, the pulsing of the precursors may use pulsingperiods that provide uniform coverage of a monolayer on the surface ormay use pulsing periods that provide partial coverage of a monolayer onthe surface during a lanthanum/oxygen ALD cycle.

In an embodiment, ALD HfO may be formed using a number of precursorscontaining hafnium to provide the hafnium to a substrate for anintegrated circuit. Such hafnium-containing precursors include, but arenot limited to, a hafnium halide, such as HfCl₄ and HfI₄, Hf(NO₃)₄,Hf[N(CH₃)(C₂H₅)]₄, Hf[N(CH₃)₂]₄, and Hf[N(C₂H₅)₂]₄. After pulsing thehafnium-containing precursor and purging the reaction chamber of excessprecursor and by-products from pulsing the precursor, an oxygen reactantprecursor may be pulsed into the reaction chamber. The oxygen reactantprecursor may include, but is not limited to, one or more of water,atomic oxygen, molecular oxygen, ozone, hydrogen peroxide, awater—hydrogen peroxide mixture, alcohol, or nitrous oxide. In addition,the pulsing of the precursors may use pulsing periods that provideuniform coverage of a monolayer on the surface or may use pulsingperiods that provide partial coverage of a monolayer on the surfaceduring a during an ALD cycle forming HfO.

In various embodiments, nitrogen may be used as a purging gas and acarrier gas for one or more of the sequences. Alternatively, hydrogen,argon gas, or other inert gases may be used as the purging gas. Excessprecursor gas and reaction by-products may be removed by the purge gas.Excess precursor gas and reaction by-products may be removed byevacuation of the reaction chamber using various vacuum techniques.Excess precursor gas and reaction by-products may be removed by thepurge gas and by evacuation of the reaction chamber.

FIG. 3 shows a flow diagram of features of an embodiment for formingHfLnON using atomic layer deposition and oxidation. At 310, a layer ofHfN is formed by atomic layer deposition. At 320, a layer of LnN isformed by atomic layer deposition on the layer of HfN. HfN and LnN filmsmay be alternately deposited in adjacent layers, in which either nitridelayer may be deposited as the starting layer. At 330, the layers of LnNand HfN are annealed. At 340, the annealed layers of LnN and HfN areoxidized to form HfLnON. In an embodiment, the annealing and oxidationmay be performed together. The layers of LnN and HfN may be annealed andoxidized by rapid thermal oxidation to form HfLnON.

In an embodiment, ALD HfN may be formed using a number of precursorscontaining hafnium to provide the hafnium to a substrate for anintegrated circuit. To form hafnium nitride by atomic layer deposition,a hafnium-containing precursor is pulsed onto a substrate in an ALDreaction chamber. A number of precursors containing hafnium may be usedto provide the hafnium to a substrate for an integrated circuit. Thehafnium-containing precursor may be a hafnium halide precursor, such asHfCl₄ or HfI₄. In addition to halide precursors, the hafnium nitride maybe grown by ALD using Hf[N(CH₃)(C₂H₅)]₄. In an embodiment, the substratemay be held at a temperature ranging from about 150° C. to about 300° C.Other types of tetrakis(dialkylamino) metal compounds may also be used,such as hafnium tetrakis dimethylamine, Hf[N(CH₃)₂]₄, or hafniumtetrakis diethylamine, Hf[N(C₂H₅)₂]₄, as a hafnium-containing precursor.In various embodiments, after pulsing the hafnium-containing precursorand purging the reaction chamber of excess precursor and by-productsfrom pulsing the precursor, a reactant precursor may be pulsed into thereaction chamber. The reactant precursor may be a nitrogen reactantprecursor including, but not limited to, ammonia (NH₃). Other nitrogenreactant precursors that may be used include nitrogen-containingcompositions that do not include oxygen. In various embodiments, use ofthe individual hafnium-containing precursors is not limited to thetemperature ranges of the above embodiments. Further, forming hafniumnitride by atomic layer deposition is not limited to the abovementionedprecursors. In addition, the pulsing of the hafnium precursor may use apulsing period that provides uniform coverage of a monolayer on thesurface or may use a pulsing period that provides partial coverage of amonolayer on the surface during a hafnium sequence.

In an embodiment, ALD LaN may be formed using a number of precursorscontaining lanthanum to provide the lanthanum to a substrate for anintegrated circuit. Such lanthanum-containing precursors include, butare not limited to, La(thd)₃, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)lanthanum (III) tetraglymeadduct, La(EtCp)₃, and La(DPM)₃. In an embodiment using a La(thd)₃precursor, the substrate may be maintained at a temperature ranging from180° C. to about 425° C. In an embodiment, H₂ may be pulsed along withthe La(EtCp)₃ precursor or the precursor to reduce carbon contaminationin the deposited film. After pulsing the lanthanum-containing precursorand purging the reaction chamber of excess precursor and by-productsfrom pulsing the precursor, a reactant precursor may be pulsed into thereaction chamber. To form LaN, a nitrogen reactant precursor is pulsed.A number of precursors containing nitrogen may be used to providenitrogen. Such nitrogen-containing precursors include, but are notlimited to, nitrogen, ammonia (NH₃), tert-butylamine (C₄H, N),allylamine (C₃H₇N), 1,1-dimethylhydrazine ((CH₃)₂NNH₂). In anembodiment, the substrate is maintained at a temperature ranging fromabout 400° C. to about 500° C. using tert-butylamine or allylamine as anitrogen precursor. In an embodiment, NH₃ may be pulsed with thetert-butylamine and the allylamine. The addition of NH₃ may enhance thedeposition rate at lower temperatures. In various embodiments, use ofthe individual lanthanum-containing precursors is not limited to thetemperature ranges of the above example embodiments. Further, forminglanthanum nitride by atomic layer deposition is not limited to theabovementioned precursors. In addition, the pulsing of the lanthanumprecursor may use a pulsing period that provides uniform coverage of amonolayer on the surface or may use a pulsing period that providespartial coverage of a monolayer on the surface during alanthanum/nitrogen sequence.

In various embodiments, nitrogen may be used as a purging gas and acarrier gas for one or more of the sequences. Alternatively, hydrogen,argon gas, or other inert gases may be used as the purging gas. Excessprecursor gas and reaction by-products may be removed by the purge gas.Excess precursor gas and reaction by-products may be removed byevacuation of the reaction chamber using various vacuum techniques.Excess precursor gas and reaction by-products may be removed by thepurge gas and by evacuation of the reaction chamber.

FIG. 4 shows a flow diagram of features of an embodiment for formingHfLnON using atomic layer deposition and annealing. At 410, a layer ofHfON is formed using atomic layer deposition. At 420, a layer of LnON isformed using atomic layer deposition on the layer of HfON. At 430, thelayers of HfON and LnON are annealed to form a layer of HfLnON. HfON andLnON films may be alternately deposited in adjacent layers, in whicheither oxynitride layer may be deposited as the starting layer.

In an embodiment, ALD LaON may be formed using a number of precursorscontaining lanthanum to provide the lanthanum to a substrate for anintegrated circuit. Such lanthanum-containing precursors include, butare not limited to, La(thd)₃, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)lanthanum (III) tetraglymeadduct, La(EtCp)₃, and La(DPM)₃. After pulsing the lanthanum-containingprecursor and purging the reaction chamber of excess precursor andby-products from pulsing the precursor, a reactant precursor may bepulsed into the reaction chamber. A nitrogen reactant precursor may bepulsed. A number of precursors containing nitrogen may be used toprovide nitrogen. Such nitrogen-containing precursors include, but arenot limited to, nitrogen, ammonia (NH₃), tert-butylamine (C₄H₁₁N),allylamine (C₃H₇N), 1,1-dimethylhydrazine ((CH₃)₂NNH₂). After pulsingthe nitrogen-containing precursor and purging the reaction chamber ofexcess precursor and by-products from pulsing the precursor, an oxygenreactant precursor may be pulsed into the reaction chamber. The oxygenreactant precursor may include, but is not limited to, one or more ofwater, atomic oxygen, molecular oxygen, ozone, hydrogen peroxide, awater—hydrogen peroxide mixture, alcohol, or nitrous oxide. In variousembodiments, the order of pulsing the precursors may vary. In variousembodiments, forming lanthanum oxynitride by atomic layer deposition isnot limited to the abovementioned precursors. In addition, the pulsingof the precursors may use pulsing periods that provide uniform coverageof a monolayer on the surface or may use pulsing periods that providepartial coverage of a monolayer on the surface during an ALD cycleforming LaON.

In an embodiment, ALD HfON may be formed using a number of precursorscontaining hafnium to provide the hafnium to a substrate for anintegrated circuit. Such hafnium-containing precursors include, but arenot limited to, a hafnium halide, such as HfCl₄ or HfI₄,Hf[N(CH₃)(C₂H₅)]₄, hafnium tetrakis dimethylamine, Hf[N(CH₃)₂]₄, orhafnium tetrakis diethylamine, Hf[N(C₂H₅)₂]₄. In various embodiments,after pulsing the hafnium-containing precursor and purging the reactionchamber of excess precursor and by-products from pulsing the precursor,a nitrogen reactant precursor may be pulsed into the reaction chamber. Anumber of precursors containing nitrogen may be used to providenitrogen. In an embodiment, NH₃ may be used as the nitrogen-containingprecursor. Other nitrogen reactant precursors that may be used includenitrogen-containing compositions that do not include oxygen. In anembodiment, the nitrogen-containing precursor may also include oxygen.After pulsing the nitrogen-containing precursor and purging the reactionchamber of excess precursor and by-products from pulsing the precursor,an oxygen reactant precursor may be pulsed into the reaction chamber.The oxygen reactant precursor may include, but is not limited to, one ormore of water, atomic oxygen, molecular oxygen, ozone, hydrogenperoxide, a water—hydrogen peroxide mixture, alcohol, or nitrous oxide.In various embodiments, the order of pulsing the precursors may vary.Further, forming hafnium oxynitride by atomic layer deposition is notlimited to the abovementioned precursors. In addition, the pulsing ofthe precursors may use pulsing periods that provide uniform coverage ofa monolayer on the surface or may use pulsing periods that providepartial coverage of a monolayer on the surface during an ALD cycleforming HfON.

In various embodiments, nitrogen may be used as a purging gas and acarrier gas for one or more of the sequences. Alternatively, hydrogen,argon gas, or other inert gases may be used as the purging gas. Excessprecursor gas and reaction by-products may be removed by the purge gas.Excess precursor gas and reaction by-products may be removed byevacuation of the reaction chamber using various vacuum techniques.Excess precursor gas and reaction by-products may be removed by thepurge gas and by evacuation of the reaction chamber.

In various embodiments, either before or after forming a HfLnON film,other dielectric layers such as HfO, LnO, HfON, LnON, dielectric nitridelayers, dielectric metal silicates, insulating metal oxides, orcombinations thereof are formed as part of a dielectric layer ordielectric stack. In an embodiment, these one or more other layers ofdielectric material may be provided in stoichiometric form, innon-stoichiometric form, or a combination of stoichiometric dielectricmaterial and non-stoichiometric dielectric material. In an embodiment,depending on the application, a dielectric stack containing a HfLnON_(x)film includes a silicon oxide layer. In an embodiment, the dielectriclayer is formed as a nanolaminate. An embodiment of a nanolaminateincludes a layer of a hafnium oxide and a HfLnON_(x) film, a layer ofhafnium oxynitride and a HfLnON_(x) film, a layer of lanthanide oxideand a HfLnON_(x) film, a layer of lanthanide oxynitride and a HfLnON_(x)film, layers of hafnium oxide, lanthanide oxide, hafnium oxynitride, andlanthanide oxynitride along with a HfLnON_(x) film, or various othercombinations. In an embodiment, a dielectric layer is formedsubstantially as the hafnium lanthanide oxynitride film.

In various embodiments, the structure of an interface between adielectric layer and a substrate on which it is disposed is controlledto limit the inclusion of silicon oxide, since a silicon oxide layerwould reduce the effective dielectric constant of the dielectric layer.In an embodiment, the material composition and properties for aninterface layer are dependent on process conditions and the condition ofthe substrate before forming the dielectric layer. In an embodiment,though the existence of an interface layer may effectively reduce thedielectric constant associated with the dielectric layer and itssubstrate, the interface layer, such as a silicon oxide interface layeror other composition interface layer, may improve the interface density,fixed charge density, and channel mobility of a device having thisinterface layer.

In an embodiment, a hafnium lanthanide oxynitride layer is doped withother elements. The doping may be employed to enhance the leakagecurrent characteristics of the dielectric layer containing theHfLnON_(x) film by providing a disruption or perturbation of the hafniumlanthanide oxynitride structure. In an embodiment, such doping isrealized by substituting a sequence of one of these elements for ahafnium sequence, a lanthanide sequence, or various combinations ofsequences. The choice for substitution may depend on the form of thehafnium lanthanide oxynitride structure with respect to the relativeamounts of hafnium atoms and lanthanide atoms desired in the oxide. Inan embodiment, to maintain a substantially hafnium lanthanideoxynitride, the amount of dopants inserted into the oxynitride arelimited to a relatively small fraction of the total number of hafniumand lanthanide atoms.

After forming a dielectric having a hafnium lanthanide oxynitride layer,other material may be formed upon the hafnium lanthanide oxynitridelayer. In an embodiment, the other material is a conductive material.The conductive material may be used as an electrode. Such electrodes maybe used as capacitor electrodes, control gates in transistors, orfloating gates in floating gate transistors. In an embodiment, theconductive material is a metal or conductive metal nitride. In anembodiment, the conductive material is a conductive semiconductormaterial. In an embodiment, the conductive material is formed by ALDprocesses. In an embodiment, the conductive material is formed by asubstitution process. In an embodiment, the conductive material isformed in a self-alignment process.

In various embodiments, a conductive layer may be deposited by atomiclayer deposition on a layer of HfLnON or on a dielectric layercontaining a layer of HfLnON. A metal layer may be deposited by atomiclayer deposition in an ALD cycle having a halide precursor containingthe metal to be deposited and a reactant precursor containing hydrogen.Metal layer formation by ALD is not limited to halide precursors andhydrogen reactant precursors. In various embodiments, precursors may beselected to form ALD conductive layers such as aluminum (Al), tungsten(W), molybdenum (Mo), gold (Au), silver (Ag), gold alloy, silver alloy,copper (Cu), platinum (Pt), rhenium (Re), ruthenium (Ru), rhodium (Rh),nickel (Ni), osmium (Os), palladium (Pd), iridium (Ir), cobalt (Co),germanium (Ge), or metallic nitrides such as WN, TiN or TaN. Formationof ALD conductive layers is not limited to the abovementioned materials.

In an example embodiment, a tantalum layer may be formed on a HfLnONfilm by atomic layer deposition using a tantalum-containing precursor.In an embodiment, a tantalum halide precursor may be used with hydrogenas a reactant precursor. In an embodiment, a TaCl₅ precursor may be usedwith an atomic hydrogen reactant precursor. The atomic hydrogen reactantprecursor may be provided using a plasma. In an embodiment, thesubstrate temperature may be held at a temperature ranging from about250° C. to about 400° C. The hydrogen reactant precursor reacts at thesubstrate to remove the halogen, which forms the selected tantalumhalide precursor, leaving tantalum on the substrate surface. Afterpulsing a tantalum-containing precursor and after pulsing its reactantprecursor, the reaction chamber may be purged of excess precursor and/orby-products. In various embodiments, use of the individualtantalum-containing precursors is not limited to the temperature rangesof the above example embodiments. Further, forming tantalum by atomiclayer deposition is not limited to the abovementioned precursors. Inaddition, the pulsing of the tantalum precursor may use a pulsing periodthat provides uniform coverage of a monolayer on the surface or may usea pulsing period that provides partial coverage of a monolayer on thesurface. The tantalum layer may be structured as one or more monolayers.The tantalum layer may have a thickness ranging from a monolayer tothousands of angstroms or more.

In an embodiment, a metal nitride layer may be deposited by atomic layerdeposition using a precursor containing the metal to be deposited and areactant precursor containing nitrogen in an ALD cycle. In an exampleembodiment, a titanium nitride layer may be formed with a HfLnON film byatomic layer deposition using a titanium-containing precursor. Anitrogen-containing precursor may be used as the reactant precursor forthe titanium-containing precursor. The titanium-containing precursor andthe nitrogen-containing precursor may be selected such that their usedoes not form a titanium oxide in the layer of titanium nitride beingformed. The titanium-containing precursor and the nitrogen-containingprecursor may be selected such that these precursors do not includeoxygen as an elemental component. In an embodiment, a titanium halideprecursor may be used with NH₃ as a reactant precursor. In anembodiment, a TiCl₄ precursor may be used with a NH₃ reactant precursor.In an embodiment, the substrate temperature may be held at a temperatureranging from about 380° C. to about 500° C. In an embodiment, thesubstrate temperature may be held at a temperature less than 600° C.After pulsing a titanium-containing precursor and after pulsing itsreactant precursor, the reaction chamber may be purged of excessprecursor and/or by-products. In various embodiments, use of theindividual titanium-containing precursors is not limited to thetemperature ranges of the above example embodiments. Further, formingtitanium nitride by atomic layer deposition is not limited to theabovementioned precursors, but may include precursors containing oxygen.In addition, the pulsing of the titanium precursor may use a pulsingperiod that provides uniform coverage of a monolayer on the surface ormay use a pulsing period that provides partial coverage of a monolayeron the surface. The titanium nitride layer may be structured as one ormore monolayers. The titanium nitride layer may have a thickness rangingfrom a monolayer to thousands of angstroms or more.

FIGS. 5A-5E illustrate an embodiment of a process for forming a metalsubstituted electrode in place of a previously deposited material on adielectric containing HfLnON. Though a transistor is discussed withreference to FIGS. 5A-5E, such a process may be used with respect toother embodiments of device configurations. FIG. 5A shows a substrate501 and shallow trench isolation (STI) regions 502. The substrate 501can be a semiconductor wafer as well as structures having one or moreinsulative, semi-insulative, conductive, or semiconductive layers andmaterials. Thus, for example, the substrate can includesilicon-on-insulator, silicon-on-sapphire, and other structures uponwhich semiconductor devices are formed.

FIG. 5B further shows a gate dielectric layer 503 formed on thesubstrate 501, and a gate substitutable layer 504 formed on the gatedielectric layer 503. The gate dielectric layer may include a dielectriclayer containing HfLnON in addition to other insulative material or adielectric layer essentially of HfLnON. The use of such a high-κdielectric increases the capacitance, which is useful for nanoscaleintegrated circuits. In various embodiments the gate dielectric includesstacked layers comprising one or more high-κ dielectric materials. Asdescribed in more detail below, the material of the gate substitutablelayer 504 is selected with respect to the desired gate material to allowthe gate material to replace the gate substitutable layer. This processforms a gate of the desired gate metal where the substitutable materialwas positioned on the gate dielectric.

As shown in FIG. 5C, portions of the gate dielectric layer 503 and thegate substitutable layer 504 are removed to define a gate 505. Sidewallsor spacers 506 are formed along the gate 505. Source/drain regions 507are also formed. Source/drain regions 507 can be formed usingconventional ion implantation and subsequent annealing. These annealingtemperatures can pose problems for aluminum gates and other metal gatesthat have melting temperatures less than the anneal temperature for thesource/drain regions.

FIG. 5D shows an insulative fill layer 508 provided to match thethickness of the gate stack. A planarization procedure, such aschemical-mechanical polishing, can be used to provide an even surfaceacross the fill layer 508 and the gate substitutable layer 504. A metallayer 509, formed of material intended to be the gate material, isdeposited over the gate substitutable layer 504 and the fill layer 508.The metal layer 509 is also referred to herein as a layer of gatematerial. Various deposition processes, such as evaporation, sputtering,chemical vapor deposition, or atomic layer deposition, may be used toform the metal layer 509. The volume of layer 509 is significantlylarger than the volume of the substitutable material left on the wafer.

After the metal layer 509 is deposited on the gate substitutable layer,a metal-substitution reaction is induced. The reaction can be providedby annealing the structure in a non-oxidizing atmosphere such as anitrogen gas or a forming gas. The heating urges diffusion ordissolution of the intended gate material in metal layer 509 for thesubstitutable material 504. The substitution process is bounded by thespacers 506 and the gate dielectric 503.

At the conclusion of the substitution reaction, the residual metal oflayer 509 and the substitutable material may be removed such as may beachieved using conventional planarization. FIG. 5E shows the resultinglow-resistance gate structure. The illustrated structure includes ametal substituted gate 510 formed by the substitution of the metal oflayer 509. The metal substituted gate 510 may include a small amount ofthe gate substitutable material that did not diffuse above theplanarization level 511. Such small amounts of the gate substitutablematerial do not significantly affect the conductivity of the metalsubstituted gate 510, and thus do not significantly affect theperformance of the device.

Drain and source contacts (not shown) can be formed, as well asinterconnects to other transistors or components, using conventionaltechniques. Another heat treatment may occur after packaging theintegrated circuit in a protective housing in an attempt to reduce theresistivity of the metal gate contacts and other metal interconnections.

The metal gate substitution technique, as disclosed herein, can beapplied to MOS devices, as generally illustrated in FIG. 5E, as well asto form metal floating gates and/or metal control gates in nonvolatiledevices. Additionally, various high-κ dielectrics having a HfLnON filmcan be used between the floating gate and the substrate, and between thecontrol gate and the floating gate in these nonvolatile devices.

FIG. 6 illustrates a flow diagram of features of an embodiment of ametal substitution technique. At 612, a gate dielectric is formed on asubstrate. The gate dielectric includes a HfLnON film. At 613, a layerof gate substitutable material is formed on the gate dielectric.Examples of gate substitutable material include polysilicon, germanium,silicon-germanium, and carbon. At 614, source/drain regions are formed.A layer of gate material is formed at 615 on the gate substitutablematerial. Examples of such metals include gold, silver, and aluminum.Other metals may be used. At 616, the gate material is substituted forthe layer of gate substitutable material.

A metal substitution reaction substitutes or replaces the substitutablematerial (e.g. silicon, germanium, silicon-germanium, carbon) with ametal. After the substitution, the resulting gate structure includessubstantially all of the desired metal. Small amounts of thesubstitutable material may remain in the gate structure. Thesubstitution reaction can be induced by heating the integrated circuitassembly to a desired temperature in a vacuum, nitrogen, argon, forminggas or other non-oxidizing atmosphere. Heating causes diffusion of themetal layer 609 into the substitutable layer. The annealing temperaturefor the substitution is less than the eutectic (lowest melting)temperature of materials involved in the substitution for the reactionfor substitution to occur. In an embodiment, to form a gold gate, ametal layer may be formed from gold and annealed at approximately 300°C. to substitute the gold for a silicon substitutable structure. In anembodiment, to form a silver gate, a metal layer may be formed fromsilver and annealed at approximately 500-600° C. to substitute thesilver for a silicon substitutable structure. A polysilicon andgermanium substitutable material may be used, which reduces the annealtemperature.

According to various embodiments, the gate substitutable material 504shown in FIGS. 5A-5E includes polysilicon. In some embodiments, the gatesubstitutable material includes germanium. Some embodiments usesilicon-germanium with a percentage of silicon in the range from 0% to100% as the gate substitutable material 504. Some embodiments use carbonas the gate substitutable material 504. With respect to variousembodiments which use polysilicon, germanium, or silicon-germanium asthe gate substitutable material 504, a replacement metal for thesubstituted gate may include aluminium, silver, gold, an alloy ofsilver, an alloy of gold as the replacement metal, or combinationsthereof. In various embodiments, with carbon used as the gatesubstitutable material 504, a replacement metal for the substituted gatemay include gold, silver, an alloy of gold, an alloy of silver, copper,platinum, rhenium, ruthenium, rhodium, nickel, osmium, palladium,iridium, cobalt, germanium, or combinations thereof.

Various embodiments form an integrated circuit structure using two ormore substitution reactions. Relatively higher temperature substitutionprocesses can be performed before relatively lower temperaturesubstitution processes. One application for multiple substitutionreactions is to independently adjust work functions of NMOS and PMOStransistors in CMOS integrated circuits. Multiple substitution reactionsare not limited to this CMOS integrated circuit application. Additionalinformation regarding metal substitution can be found in U.S. patentapplication Ser. No. 11/176,738 filed Jul. 7, 2005, entitled“METAL-SUBSTITUTED TRANSISTOR GATES,” which is herein incorporated byreference.

FIGS. 7A-7D illustrate an embodiment of a process for forming a selfaligned conductive layer such as a metal gate for a transistorstructure. FIG. 7A illustrates a high-κ gate dielectric 710 containingHfLnON formed on a substrate 701. The substrate 701 can be asemiconductor wafer as well as structures having one or more insulative,semi-insulative, conductive, or semiconductive layers and materials.Thus, for example, the substrate can include silicon-on-insulator,silicon-on-sapphire, and other structures upon which semiconductordevices are formed.

In FIG. 7A, a sacrificial gate 703 is formed of amorphous carbon on thehigh-κ gate dielectric 710. In various embodiments, an etch barrier 708is formed over the sacrificial gate and the dielectric. The etch barrier708 includes silicon nitride or aluminium oxide, and can be formed usinga deposition process, according to various embodiments. Sacrificialsidewall spacers 706 are added adjacent the sacrificial gate 703. Invarious embodiments, the spacers 706 are formed of amorphous carbon bydeposition and conventional direct etch techniques. An ion implantation730 and high temperature anneal are used to form source/drain regions702 in areas defined by the sacrificial sidewall spacers 706. Theseannealing temperatures can pose problems for aluminum gates and othermetal gates that have melting temperatures less than the annealtemperature for the source/drain regions.

In FIG. 7B, the sacrificial sidewall spacers (706 in FIG. 7A) have beenremoved. Various embodiments use a plasma oxidation process to removethe sacrificial sidewall spacers. In addition, the etch barrier (708 inFIG. 7A) has been removed. In various embodiments, a light dose ionimplantation 740 is used to form source/drain extensions 742 in thesubstrate 701. The extensions 742 can be annealed at lower temperaturesand in shorter times than the more heavily doped source/drain regions702. According to various embodiments, source/drain extensions for thetransistor may be formed with doping the substrate to a depth of 30 nmor less.

In FIG. 7C, conventional or non-carbon sidewall spacers 756 are formedand the whole structure is back filled with an oxide fill 758, such assilicon dioxide, and planarized. A planarization procedure, such aschemical-mechanical polishing, can be used to provide an even surface.In various embodiments, the conventional sidewall spacers are formedwith silicon nitride.

In FIG. 7D, the sacrificial gate (703 in FIG. 7C) is removed andreplaced by the deposition of a metal layer 760. In various embodiments,the sacrificial gate is removed using a plasma oxidation process.Various deposition processes, such as evaporation, sputtering, chemicalvapor deposition, or atomic layer deposition, may be used to form themetal layer 760. The structure is planarized (not shown) using aplanarization procedure, such as chemical-mechanical polishing,resulting in the self aligned metal gate over the high-κ gate dielectricinsulator 710. Drain and source contacts (not shown) can be formed, aswell as interconnects to other transistors or components, usingconventional techniques. Another heat treatment may occur afterpackaging the integrated circuit in a protective housing in an attemptto reduce the resistivity of the metal gate contacts and other metalinterconnections.

FIGS. 7A-7D illustrate two replacement processes for the formation ofplanar self aligned metal gate transistors, one for disposable sidewallspacers and the other for the gate material itself. The metal gatereplacement technique, as disclosed herein, can be applied to MOSdevices, as generally illustrated in FIGS. 7A-7D, as well as to formmetal floating gates and/or metal control gates in nonvolatile devices.Additionally, various high-κ dielectrics can be used between thefloating gate and the substrate, and between the control gate and thefloating gate in these nonvolatile devices.

FIG. 8 illustrates an embodiment of a method 800 for forming a selfaligned metal gate on high-κ gate dielectrics containing HfLnON.According to various embodiments, a high-κ gate dielectric containingHfLnON is formed on a substrate, at 802. At 804, a sacrificial carbongate is formed on the gate dielectric. At 806, sacrificial carbonsidewall spacers are formed adjacent to the sacrificial carbon gate. At808 source/drain regions for the transistor are formed, using thesacrificial carbon sidewall spacers to define the source/drain regions.The sacrificial carbon sidewall spacers are replaced with non-carbonsidewall spacers at 810. At 812, the sacrificial carbon gate is replacedwith a desired metal gate material to provide the desired metal gatematerial on the gate dielectric.

In various embodiments, source/drain extensions may be formed afterremoving the carbon sidewall spacers and before replacing withnon-carbon sidewall spacers. An etch barrier is used in variousembodiments to separate the sacrificial carbon gate from the sacrificialcarbon sidewall spacers. In various embodiments, the carbon sacrificialgate may be replaced with aluminum (Al), tungsten (W), molybdenum (Mo),gold (Au), silver (Ag), gold alloy, silver alloy, copper (Cu), platinum(Pt), rhenium (Re), ruthenium (Ru), rhodium (Rh), nickel (Ni), osmium(Os), palladium (Pd), iridium (Ir), cobalt (Co), germanium (Ge), ormetallic nitrides such as WN, TiN or TaN covered by metals. The high-κgate dielectric formed at 802 may be one of a number of high-κ gatedielectrics containing HfLnON.

In various embodiments, construction of an integrated circuit structureincludes a dielectric containing HfLnON on which is disposed aself-aligned metal electrode. Additional information regarding aself-aligned metal electrode used as a transistor gate can be found inU.S. patent application Ser. No. 11/216,375, filed 31 Aug. 2005,entitled “SELF ALIGNED METAL GATES ON HIGH-K DIELECTRICS,” which isherein incorporated by reference.

FIG. 9 illustrates an embodiment of a wafer 940 containing integratedcircuits having one or more dielectric layers that include a hafniumlanthanide oxynitride film. Conductive electrodes may be disposed onsuch dielectrics in a number of configurations such as capacitors,transistors, or elements of a memory. The conductive electrodes may bemetal electrodes, conductive metal nitride electrodes, and/or conductivemetal oxide electrodes. The conductive electrodes may be atomic layerdeposited electrodes. Metal electrodes may be metal substitutedelectrodes and/or self aligned metal electrodes formed in accordancewith the teachings of embodiments discussed herein. A common wafer sizeis 8 inches in diameter. However, wafers are capable of being fabricatedin other sizes, and embodiments of wafers containing a hafniumlanthanide oxynitride film are not limited to a particular size. Anumber of dies can be formed on a wafer. A die 941 is an individualpattern on a substrate that contains circuitry to perform a specificfunction. A semiconductor wafer typically contains a repeated pattern ofsuch dies containing the same functionality. A die is typically packagedin a protective casing (not shown) with leads extending therefrom (notshown) providing access to the circuitry of the die for communicationand control.

Applications containing electronic devices having dielectric layerscontaining hafnium lanthanide oxynitride film include electronic systemsfor use in memory modules, device drivers, power modules, communicationmodems, processor modules, and application-specific modules, which mayinclude multilayer, multichip modules. Such dielectric layers may beconfigured as multiple layers containing at least one layer of HfLnON orconfigured substantially as a HfLnON layer. In addition, such dielectriclayers may be configured in contact with a metal electrode. Suchcircuitry can be a subcomponent of a variety of electronic systems, suchas a clock, a television, a cell phone, a personal computer, anautomobile, an industrial control system, an aircraft, and others.

FIG. 10 shows an embodiment of a transistor 1000 having a dielectriclayer 1040 containing a HfLnON_(x) film. In an embodiment, transistor1000 includes a source region 1020 and a drain region 1030 in asilicon-based substrate 1010 where source and drain regions 1020, 1030are separated by a body region 1032. Body region 1032 defines a channelhaving a channel length 1034. In an embodiment, a gate dielectric 1040is disposed on substrate 1010 with gate dielectric 1040 formed as adielectric layer containing HfLnON_(x). In an embodiment, gatedielectric 1040 is realized as a dielectric layer formed substantiallyof HfLnON_(x). In an embodiment, gate dielectric 1040 is constructed asmultiple dielectric layers, that is, as a dielectric stack, containingat least one HfLnON_(x) film and one or more layers of insulatingmaterial other than hafnium lanthanide oxynitride film. In anembodiment, the HfLnON_(x) film is structured as one or more monolayers.An embodiment of a HfLnON_(x) film is formed using atomic layerdeposition. In an embodiment, gate dielectric 1040 may be realized as agate insulator in a silicon-based structure.

In an embodiment, a gate 1050 is formed on and contacts gate dielectric1040. In an embodiment, gate 1050 includes conductive material. In anembodiment, gate 1050 includes a conductive material structured as oneor more monolayers. In an embodiment, the conductive material layer isan ALD conductive material layer. In an embodiment, the conductivematerial layer is a substituted metal layer. In an embodiment, theconductive material layer is a self-aligned metal layer. In anembodiment, the thickness of the conductive layer ranges from amonolayer to thousands of angstroms or more.

An interfacial layer may form between body region 1032 and gatedielectric 1040. In an embodiment, an interfacial layer is limited to arelatively small thickness compared to gate dielectric 1040, or to athickness significantly less than gate dielectric 1040 as to beeffectively eliminated. In an embodiment, forming the substrate and thesource and drain regions is performed using processes known to thoseskilled in the art. In an embodiment, the sequencing of the variouselements of the process for forming a transistor is conducted withfabrication processes known to those skilled in the art. In anembodiment, transistor 1000 is a MOSFET transistor. In an embodiment,transistor 1000 is a germanium MOSFET structure. In an embodiment,transistor 1000 is a silicon MOSFET structure. In an embodiment,transistor 1000 is a silicon-germanium (SiGe) MOSFET structure. In anembodiment, transistor 1000 is a gallium arsenide MOSFET structure. Inan embodiment, transistor 1000 is a NMOS transistor. In an embodiment,transistor 1000 is a PMOS transistor. Transistor 1000 is not limited tothe arrangement illustrated in FIG. 10. For example, transistor 1000 maybe structured as a vertical transistor. In various embodiments, use of agate dielectric containing hafnium lanthanide oxynitride is not limitedto silicon-based substrates, but is used with a variety of semiconductorsubstrates.

FIG. 11 shows an embodiment of a floating gate transistor 1100 having adielectric layer containing a HfLnON_(x) film. In an embodiment, theHfLnON_(x) film is structured as one or more monolayers. In anembodiment, the HfLnON_(x) film is formed using atomic layer depositiontechniques. In an embodiment, transistor 1100 includes a silicon-basedsubstrate 1110 with a source 1120 and a drain 1130 separated by a bodyregion 1132. Body region 1132 between source 1120 and drain 1130 definesa channel region having a channel length 1134. Located above body region1132 is a stack 1155 including a gate dielectric 1140, a floating gate1152, a floating gate dielectric 1142 (integrate dielectric 1142), and acontrol gate 1150. An interfacial layer may form between body region1132 and gate dielectric 1140. In an embodiment, such an interfaciallayer is limited to a relatively small thickness compared to gatedielectric 1140 or to a thickness significantly less than gatedielectric 1140 as to be effectively eliminated.

In an embodiment, gate dielectric 1140 includes a dielectric containingan atomic layer deposited HfLnON_(x) film formed in embodiments similarto those described herein. In an embodiment, gate dielectric 1140 isrealized as a dielectric layer formed substantially of HfLnON_(x). In anembodiment, gate dielectric 1140 is a dielectric stack containing atleast one HfLnON_(x) film and one or more layers of other insulatingmaterials.

In an embodiment, floating gate 1152 is formed on and contacts gatedielectric 1140. In an embodiment, floating gate 1152 includesconductive material. In an embodiment, floating gate 1152 is structuredas one or more monolayers. In an embodiment, floating gate 1152 is anALD layer. In an embodiment, floating gate 1152 is a substituted metallayer. In an embodiment, floating gate 1152 is a self-aligned metallayer. In an embodiment, the thickness of the floating gate layer rangesfrom a monolayer to thousands of angstroms or more.

In an embodiment, floating gate dielectric 1142 includes a dielectriccontaining a HfLnON_(x) film. In an embodiment, the HfLnON_(x) film isstructured as one or more monolayers. In an embodiment, the HfLnON_(x)is formed using atomic layer deposition techniques. In an embodiment,floating gate dielectric 1142 is realized as a dielectric layer formedsubstantially of HfLnON_(x). In an embodiment, floating gate dielectric1142 is a dielectric stack containing at least one HfLnON_(x) film andone or more layers of other insulating materials.

In an embodiment, control gate 1150 is formed on and contacts floatinggate dielectric 1142. In an embodiment, control gate 1150 includesconductive material. In an embodiment, control gate 1150 is structuredas one or more monolayers. In an embodiment, the control gate 1150 is anALD layer. In an embodiment, control gate 1150 is a substituted metallayer. In an embodiment, control gate 1150 is a self-aligned metallayer. In an embodiment, the thickness of the control gate layer 1150ranges from a monolayer to thousands of angstroms or more. In anembodiment, control gate 1150 is structured as one or more monolayers.

In an embodiment, both gate dielectric 1140 and floating gate dielectric1142 are formed as dielectric layers containing a HfLnON_(x) filmstructured as one or more monolayers. In an embodiment, control gate1150 and floating gate 1152 are formed as conductive layers. In anembodiment, the control gate 1150 and floating gate 1152 are structuredas one or more monolayers. In an embodiment, control gate 1150 andfloating gate 1152 are ALD layers. In an embodiment, control gate 1150and floating gate 1152 are substituted metal layers. In an embodiment,control gate 1150 and floating gate 1152 are self-aligned metal layers.In an embodiment, gate dielectric 1140, floating gate dielectric 1142,control gate 1150, and floating gate 1152 are realized by embodimentssimilar to those described herein, with the remaining elements of thetransistor 1100 formed using processes known to those skilled in theart. In an embodiment, gate dielectric 1140 forms a tunnel gateinsulator and floating gate dielectric 1142 forms an inter-gateinsulator in flash memory devices, where gate dielectric 1140 andfloating gate dielectric 1142 may include an hafnium lanthanideoxynitride film structured as one or more monolayers. Floating gatetransistor 1100 is not limited to the arrangement illustrated in FIG.11. For example, floating gate transistor 1100 may be structured as avertical transistor. Such structures are not limited to silicon-basedsubstrates, but may be used with a variety of semiconductor substrates,such as for but not limited to germanium floating gate transistors, SiGefloating gate transistors, and gallium arsenide floating gatetransistors.

FIG. 12 shows an embodiment of a capacitor 1200 having a dielectriclayer containing a hafnium lanthanide oxynitride film 1220 and having anelectrode 1230. Embodiments of a hafnium lanthanum oxynitride film 1220structured as one or more monolayers may also be applied to capacitorsin various integrated circuits, memory devices, and electronic systems.In an embodiment for a capacitor 1200 illustrated in FIG. 12, a methodincludes forming a first conductive layer 1210, forming a dielectriclayer 1220 containing a hafnium lanthanide oxynitride film structured asone or more monolayers on first conductive layer 1210, and forming asecond conductive layer 1230 on dielectric layer 1220. In variousembodiments, second conductive layer 1230, first conductive layer 1210,or both second and first conductive layers 1230, 1210 are ALD conductivematerial layers, substituted metal layers, self-aligned metal layers, ora combination thereof. In an embodiment, the thickness of the conductivelayer ranges from a monolayer to thousands of angstroms or more.

In an embodiment, dielectric layer 1220, containing a HfLnON_(x) film,and conductive layers 1210, 1220 are formed using various embodimentsdescribed herein. In an embodiment, dielectric layer 1220 is realized asa dielectric layer formed substantially of HfLnON_(x). In an embodiment,dielectric layer 1220 is a dielectric stack containing at least oneHfLnON_(x) film and one or more layers of other insulating materials.Embodiments for a hafnium lanthanide oxynitride film may include, butare not limited to, a capacitor in a DRAM and capacitors in analog,radio frequency (RF), and mixed signal integrated circuits. Mixed signalintegrated circuits are integrated circuits that may operate withdigital and analog signals.

FIG. 13 depicts an embodiment of a dielectric structure 1300 havingmultiple dielectric layers 1305-1, 1305-2 . . . 1305-N, in which atleast one layer is a hafnium lanthanide oxynitride layer. In anembodiment, layers 1310 and 1320 provide means to contact dielectriclayers 1305-1, 1305-2 . . . 1305-N. In an embodiment, each layer 1310,1320 or both layers are conductive layers. In an embodiment, layers 1310and 1320 are electrodes forming a capacitor. In an embodiment, layer1310 is a body region of a transistor with layer 1320 being a gate. Inan embodiment, layer 1310 is a floating gate electrode with layer 1320being a control gate.

In an embodiment, dielectric structure 1300 includes one or more layers1305-1, 1305-2 . . . 1305-N as dielectric layers other than a HfLnONlayer, where at least one layer is a HfLnON layer. In an embodiment,dielectric layers 1305-1, 1305-2 . . . 1305-N include a HfO layer, a LnOlayer, a HfON layer, a LnON layer, or various combinations of theselayers. In an embodiment, dielectric layers 1305-1, 1305-2 . . . 1305-Ninclude an insulating metal oxide layer. In an embodiment, dielectriclayers 1305-1, 1305-2 . . . 1305-N include an insulating nitride layer.In an embodiment, dielectric layers 1305-1, 1305-2 . . . 1305-N includean insulating oxynitride layer. In an embodiment, dielectric layers1305-1, 1305-2 . . . 1305-N include an insulating silicate layer.

Various embodiments for a dielectric layer containing a hafniumlanthanide oxynitride film structured as one or more monolayers mayprovide for enhanced device performance by providing devices withreduced leakage current. Such improvements in leakage currentcharacteristics may be attained by forming one or more layers of ahafnium lanthanide oxynitride in a nanolaminate structure with othermetal oxides, non-metal-containing dielectrics, or combinations thereof.The transition from one layer of the nanolaminate to another layer ofthe nanolaminate provides disruption to a tendency for an orderedstructure in the nanolaminate stack. The term “nanolaminate” means acomposite film of ultra thin layers of two or more materials in alayered stack. Typically, each layer in a nanolaminate has a thicknessof an order of magnitude in the nanometer range. Further, eachindividual material layer of the nanolaminate may have a thickness aslow as a monolayer of the material or as high as 20 nanometers. In anembodiment, a HfO/HfLnON nanolaminate contains alternating layers of aHfO and HfLnON. In an embodiment, a HfON/HfLnON nanolaminate containsalternating layers of a HfON and HfLnON. In an embodiment, a LnON/HfLnONnanolaminate contains alternating layers of LnON and HfLnON. In anembodiment, a LnO/HfLnON nanolaminate contains alternating layers of LnOand HfLnON. In an embodiment, a HfO/LnON/LnO/HfON/HfLnON nanolaminatecontains various permutations of hafnium oxide layers, lanthanideoxynitride layers, lanthanide oxide layers, hafnium oxynitride layers,and hafnium lanthanide oxynitride layers.

In an embodiment, the sequencing of the layers in dielectric structure1300 structured as a nanolaminate depends on the application. Theeffective dielectric constant associated with nanolaminate structure1300 is that attributable to N capacitors in series, where eachcapacitor has a thickness defined by the thickness and composition ofthe corresponding layer. In an embodiment, by selecting each thicknessand the composition of each layer, a nanolaminate structure isengineered to have a predetermined dielectric constant. Embodiments forstructures such as nanolaminate structure 1300 may be used asnanolaminate dielectrics in flash memory devices as well as otherintegrated circuits. In an embodiment, a layer of the nanolaminatestructure 1300 is used to store charge in a flash memory device. Thecharge storage layer of a nanolaminate structure 1300 in a flash memorydevice may be a silicon oxide layer.

In an embodiment, transistors, capacitors, and other devices includedielectric films containing a layer of a hafnium lanthanide oxynitridecomposition with an electrode. In an embodiment, the hafnium lanthanideoxynitride layer is an atomic layer deposited hafnium lanthanideoxynitride layer. In an embodiment, the electrode is an atomic layerdeposited electrode. In an embodiment, the electrode is a substitutedmetal layer. In an embodiment, the electrode is a self-aligned metallayer. In an embodiment, dielectric films containing a hafniumlanthanide oxynitride layer with an electrode are implemented intomemory devices and electronic systems including information handlingdevices. In various embodiments, information handling devices includewireless systems, telecommunication systems, and computers. In variousembodiments, such electronic devices and electronic apparatus arerealized as integrated circuits.

FIG. 14 illustrates a block diagram for an electronic system 1400 withone or more devices having a dielectric structure including a HfLnON_(x)film with an electrode. Electronic system 1400 includes a controller1405, a bus 1415, and an electronic device 1425, where bus 1415 provideselectrical conductivity between controller 1405 and electronic device1425. In various embodiments, controller 1405 includes an embodiment ofa HfLnON_(x) film with an electrode. In various embodiments, electronicdevice 1425 includes an embodiment of a HfLnON_(x) film with anelectrode. In various embodiments, controller 1405 and electronic device1425 include embodiments of a HfLnON_(x) film with an electrode. In anembodiment, electronic system 1400 includes, but is not limited to,fiber optic systems, electro-optic systems, and information handlingsystems such as wireless systems, telecommunication systems, andcomputers.

FIG. 15 depicts a diagram of an embodiment of a system 1500 having acontroller 1505 and a memory 1525. In an embodiment, controller 1505includes a HfLnON film with an electrode. In an embodiment, memory 1525includes a HfLnON film structured as one or more monolayers with anelectrode. In an embodiment, controller 1505 and memory 1525 eachinclude a HfLnON film with an electrode. In an embodiment, system 1500also includes an electronic apparatus 1535 and a bus 1515, where bus1515 provides electrical conductivity between controller 1505 andelectronic apparatus 1535 and between controller 1505 and memory 1525.In an embodiment, bus 1515 includes an address bus, a data bus, and acontrol bus, each independently configured. In an alternativeembodiment, bus 1515 uses common conductive lines for providing one ormore of address, data, or control, the use of which is regulated bycontroller 1505. In an embodiment, electronic apparatus 1535 isadditional memory configured in a manner similar to memory 1525. In anembodiment, additional peripheral device or devices 1545 are coupled tobus 1515. In an embodiment, peripheral devices 1545 include displays,additional storage memory, or other control devices that may operate inconjunction with controller 1505. In an alternative embodiment,peripheral devices 1545 may include displays, additional storage memory,or other control devices that may operate in conjunction with memory1525, or controller 1505 and memory 1525. In an embodiment, controller1505 is a processor. In an embodiment, one or more of controller 1505,memory 1525, bus 1515, electronic apparatus 1535, or peripheral devices1545 include an embodiment of a dielectric layer having a HfLnON filmstructured as one or more monolayers with an electrode. In anembodiment, system 1500 includes, but is not limited to, informationhandling devices, telecommunication systems, and computers.

In an embodiment, memory 1525 is realized as a memory device containinga HfLnON film structured as one or more monolayers with an electrode. Inan embodiment, a HfLnON structure with a conductive layer is formed in amemory cell of a memory array. In an embodiment, such a structure isformed in a capacitor in a memory cell of a memory array. In anembodiment, such a structure is formed in a transistor in a memory cellof a memory array. In an embodiment, it will be understood thatembodiments are equally applicable to any size and type of memorycircuit and are not intended to be limited to a particular type ofmemory device. Memory types include a DRAM, SRAM (Static Random AccessMemory) or Flash memories. Additionally, the DRAM could be a synchronousDRAM commonly referred to as SGRAM (Synchronous Graphics Random AccessMemory), SDRAM (Synchronous Dynamic Random Access Memory), SDRAM II, andDDR SDRAM (Double Data Rate SDRAM), as well as other emerging DRAMtechnologies.

Although specific embodiments have been illustrated and describedherein, it will be appreciated by those of ordinary skill in the artthat any arrangement that is calculated to achieve the same purpose maybe substituted for the specific embodiments shown. Various embodimentsuse permutations and/or combinations of embodiments described herein. Itis to be understood that the above description is intended to beillustrative, and not restrictive, and that the phraseology orterminology employed herein is for the purpose of description and not oflimitation.

1. A method comprising: forming a dielectric including HfLnON, thedielectric formed on a substrate of an electronic device.
 2. The methodof claim 1, wherein the method includes forming a metal electrode on andcontacting the dielectric.
 3. The method of claim 2, wherein forming ametal electrode includes forming the metal electrode by substituting adesired metal material for previously disposed substitutable material.4. The method of claim 2, wherein forming a metal electrode includesforming a self aligned metal electrode on and contacting the dielectric.5. A method comprising: forming a dielectric including HfLnON, whereinforming the HfLnON includes forming an intermediate composition havingat least two elements of HfLnON and processing the intermediatecomposition to form the HfLnON, the forming of the intermediatecomposition includes using a self-limiting monolayer or partialmonolayer sequencing process.
 6. The method of claim 5, wherein formingthe HfLnON includes forming HfLnO using the self-limiting monolayer orpartial monolayer sequencing process and nitridizing the HfLnO to formHfLnON.
 7. The method of claim 6, wherein forming HfLnO includes:forming hafnium oxide by the self-limiting monolayer or partialmonolayer sequencing process; forming lanthanide oxide by theself-limiting monolayer or partial monolayer sequencing process; andannealing the hafnium oxide with the lanthanide oxide to form HfLnO. 8.The method of claim 5, wherein forming the HfLnON includes: forming HfNby the self-limiting monolayer or partial monolayer sequencing process;forming LnN by the self-limiting monolayer or partial monolayersequencing process; and oxidizing the HfN and LnN to form HfLnON.
 9. Themethod of claim 5, wherein forming the HfLnON includes: forming HfON bythe self-limiting monolayer or partial monolayer sequencing process;forming LnON by the self-limiting monolayer or partial monolayersequencing process; and annealing the HfON with the LnON to form HfLnON.10. The method of claim 5, wherein the method includes forming a metalelectrode on and contacting the dielectric, the metal electrode formedby forming substitutable material on the dielectric, the substitutablematerial including one or more materials selected from the groupconsisting of carbon, polysilicon, germanium, and silicon-germanium, andsubstituting a desired metal material for the substitutable material toprovide the metal electrode on the dielectric.
 11. The method of claim5, wherein the method includes forming a self aligned metal electrode onand contacting the dielectric using a previously disposed sacrificialcarbon on the dielectric and sacrificial carbon sidewall spacersadjacent to the sacrificial carbon.
 12. A method comprising: forming anarray of memory cells on a substrate, each memory cell including adielectric containing HfLnON.
 13. The method of claim 12, wherein themethod includes forming the HfLnON using a self-limiting monolayer orpartial monolayer sequencing process.
 14. The method of claim 13,wherein the method includes: forming HfLnO by the self-limitingmonolayer or partial monolayer sequencing process; and nitridizing theHfLnO to form HfLnON.
 15. The method of claim 13, wherein the methodincludes: forming HfN by the self-limiting monolayer or partialmonolayer sequencing process; forming LnN by the self-limiting monolayeror partial monolayer sequencing process; annealing the HfN with the LnN;and oxidizing the HfN and the LnN to form HfLnON.
 16. The method ofclaim 13, wherein the method includes: forming HfON by the self-limitingmonolayer or partial monolayer sequencing process; forming LnON by theself-limiting monolayer or partial monolayer sequencing process; andannealing the HfON with the LnON to form HfLnON.
 17. The method of claim12, wherein the method includes forming a metal electrode on andcontacting the dielectric, forming the metal electrode including:forming a layer of substitutable material on the dielectric; andsubstituting a desired metal material for the substitutable material toprovide the metal electrode on the dielectric.
 18. An electronic devicecomprising: a substrate; and a dielectric disposed on the substrate, thedielectric containing HfLnON.
 19. The electronic device of claim 18,wherein the HfLnON is arranged as a layered structure of one or moremonolayers.
 20. The electronic device of claim 18, wherein the HfLnONincludes HfLaON.
 21. The electronic device of claim 18, wherein thedielectric includes dielectric material other than HfLnON.
 22. Theelectronic device of claim 21, wherein the dielectric material includesa metal oxide.
 23. The electronic device of claim 18, wherein thedielectric is structured as a nanolaminate.
 24. The electronic device ofclaim 18, wherein the dielectric is disposed in a memory.